Insecticidal spray materials



Patented June 23, 1936 UNITED STATES PATENT OFFICE dell H. Tisdale and Albert L. Fienner. Wilmington, Del., assimon to E. I. du Pont de Ncmours a Company,

poration oi. Delaware Wilmington. DcL, a cor- No Drawing. Application March til, W34. Serial No. 718,206

a (llainw. (c1. it'l -22) This invention relates to insecticidal spray ma terials and more particularly to new and improved insecticidal compounds.

Many insecticidal compounds have been dissolved or suspended in water and oil-in-water emulsions and similar liquid media and the resulting solutions, suspensions and emulsions have been employed as insecticidal sprays. These various spray materials have met with 1 varying degreesof success but none have proved to he entirely satisfactory for our purposes.

an object of the present invention is to provide new insecticidal spray materials. A further ob- .icct is to provide insecticidal spray materials comprising aqueous liquids having incorporated therein acid salts of organic lead compounds as the main insecticidal ingredients. Another object is to provide a method for controlling insects. Other objects are to provide new compositions of matter and to advance the art. Still other objects will appear hereinafter. I

These objects may be accomplished in accordance with. our invention which comprises incorporating, in aqueous liquids to be employed as insecticidal spray materials, acid salts oi organic lead compounds having the formula:

amrbim wherein R, represents'an unsubstituted hydrocarbon radical, m represents at least 2, n represents at least 1, and m plus n equals i. The most effective compounds of this type are those in which m represents 3. Therefore the compounds V which we prefer may be more specifically represented by the formula:

wherein R represents an unsubstituted hydrocarbon radical and X represents an acid radical. 40 The term unsubstituted hydrocarbon radical" as employed herein includes radicals such as methyl, ethyl, propyl, butyl, phenyl, tolyl, naphthyl and benzyl radicals. In other words, unsubstituted hydrocarbon radical means a radi cal consisting solely of carbon and hydrogen.

The term acid as employed herein is to he understood to have its commonly accepted meaning and not to include compounds such as phenol which have acidic properties under some conditions and are sometimes termed acids.

The most edective compounds of our elm-s are the compounds in which X in the iormu":

RcPbK represents a thiocyanic acid radical. 0i these, ill triethyl lead thiocyanate and triphenyl lead thiccyanate are preferred. Among the other compounds which we have found to be particularly satisfactory for our purpose are triethyl lead oleate, triphenyl lead cleate, triethyl lead steaw rate, triethyl lead resinate, triethyl lead nitrate, triethyl lead formats, triethyl lead aceto thiccyanate, triethyl lead dithiocarioamate, triethyl lead thioglycolate, trlethyl lead cyanide, and triethyl lead thiosulphate.

In order to more clearly illustrate our invention and the preferred modes of carrying the same into efi'ect and the advantageous results to be obtained thereby, the following examples are given: 2

Example 1 Example 3 An oil emulsion containing 3% oi triethyl lead oleate was diluted with water to form an emulsion containing one part of theoil emulsion to 200 parts of water. This diluted emulsion was sprayed on a Viburnum plant iniested with brown aphids. approximately of the aphids were killed and no injury was caused to the M3 plant.

Example 4 One part of an oil emulsion, containing 5% diethyl lead dioleate. was diluted with -parts of water and sprayed on chrysanthemum plants 0 wi 11 1000 parts of water.

infested with black aphis. This killed approximately 25% oi the aphis and caused no injury to the plant.

Example 5 One part oi. diethyl ammonium oleate, containing triethyl lead stearate. was diluted with 1000 parts of water. Upon being sprayed on ohrysanthemum plants, thismaterial killed over 05% 0! the black aphids thereon but slightly burned the plants.

Example 6 One part of a solution of 20% triethyl lead resinate in diethyl ammonium oleate was diluted This diluted solution kl led approximately 96% of black chrysanthemum aphis and caused no injury to the plants.

Example 7 Example 8 One part of triethyl lead nitrate was diluted with 4000 parts of water containing 0.1% of diethyl ammonium oleate as a wetting agent. Upon spraying chrysant-hemum plants with this diluted material, 97% of the black aphids were killed.

Example 9 One part of diethyl ammonium oleate, containing 20% trlethyl lead thiocyanate in solution, was diluted with 2000 parts of soft water. This material killed more than 97% of the chrysanthemum aphids upon being sprayed thereon. I

Example 10 One part of triethyl lead formate was diluted with 5000 parts of water containing 0.1% of diethyl ammonium oleate employed as a. spreadins agent. This material killed approximately 90% of black aphis of chrysanthemum.

Example 11 Triethyl lead aceto thiocyanate was dissolved in diethyl ammonium oleate and this solution was diluted with water; the proportions being such that, in the final material, there was one part of the lead compound for every 15,000 parts of water and one part of amine soap to every 1000 parts of water. When this material was employed as a spray, it killed approximately 90% oi black chrysanthemum aphis in 24 hours.

Example 12 One part of triethyl lead dithiocarbamate was suspended in 5000 parts of water, employing 10 parts of diethyl ammonium oleate as an emulsitier and spreading agent. This spray material killed more than 98% of black chrysanthemum aphis in 24 hours.

Example 13 one part of triethyl lead thioglycolate was diluted with 5000 parts of water containing 0.1%

of sulphonated cod oil as a spreader. This material killed approximately 05% of black chrysanthemum aphis in 24 hours.

Example 14 One part of triethyl lead cyanide was diluted with 5000 parts of water containing 0.1% of diethyl ammonium oleate as a spreader. This material killed more than 90% of green potato aphis but slightly burned the foliage.

Example 15 Exam le 16 One part of an oil emulsion containing 1.5% triethyl lead oleate was diluted with 60 parts of water and sprayed on lemons infested with red scale. More than 90% of the adult scale insects were killed. 25

. Example 17 One part of a miscible oil containing 2.5% of triethyl lead oleate when diluted with 50 parts of water and sprayed on the pupae of the coolling 30 moth, killed approximately of thepupae.

While the above examples illustrate the results to be obtained with some of our compounds it is to be understood that such examples are illustrative only and many other examples could be given without, however, serving any useful purpose, as the above examples represent the results to be obtained with the various members of our class. Accordingly, othercompounds within our class which may be employed eflectively for our purpose are more generally indicated hereinafter.

. It will be found that results similar to those shown in the examples will be obtained if other hydrocarbon radicals such as methyl, propyl, butyl, tolyl, benzyl, naphthyl and the like are substituted for the ethyl and phenyl radicals. Also, compounds, in which m and n of our formula RmPbXn represent the integer 2, will be found to be effective. Furthermore, X in our formula may represent other organic or inorganic acid radicals, than oleic, stearic, resinic, sulionated fish oil, nitric, thlocyanic, formic, aceto thiocyanic, dithiocarbamic, thioglycolic, cyanic and thiosulfuric. Some of these other acid radicals are those of palmitic, butyric, acetic, lactic, tannic, abietic, arsenic, fluosilicic, other dithiocarbamic acids, sulfuric, hydrochloric, hydrobromic and like acids. Other radicals may be introduced into the acid part 6 of the compounds to render the compounds more 7 stable and less volatile. Such radicals may be represented by the acyl radicals such as acetyl as in' aceto cyanic acid. The trihydrocarbon lead salts of these various acids will, in the 65 majority of cases, be found to be materially more eifective than other salts of these acids which have heretofore been employed for this purpose. This characteristic of our compound is particularly apparent in the triethyl and triphenyl lead 70 thiocyanates and dithiocarbamates which are materially more efiective than other thiocyanates and dithiocarbamates heretofore employed.

The organic lead suli'onates have also been found to have insecticidal properties and also 75 are generally good dispersing and wetting agents. For example. the triethyl lead sulionatesand triphenyl lead sulionates, prepared from suitonated oils such as animal, vegetable, and mineral oils, have contact insecticidal properties and are good dispersing and wetting agents. Likewise. the triethyl lead or triphenyl lead and related salts of sulionated compounds, such as lauryl sulionate, sulionated glycerol abietate, isopropyl suli'onic acid, isopropyl naphthalene sultonic acid, sulionated higher alcohols comprising mixed iractions or straight and side chain types,

and other similar sulfonated compounds which have been employed as detergents or' wetting agents, combine the properties of dispersing and wetting agents with effective insecticidal properties. These organic lead compounds oi suli'onated oils and the like are generally less efi'ective insecticides than the othercompounds of our invention but have the advantage of being Y complete within themselves and may be readily soluble in oil. These compounds are particularly I adapted for use in oil-in-water emulsions.- Other compounds of ourinvention are relatively insoluble in water and oil but are soluble in amine soaps which are good dispersing and wetting agents. '40- Such compounds may be first dissolved in the amine soaps and such solutions may be incorporated in water or in oil-in-water emulsions. Other compounds of our invention are insoluble in water, oil and the amine soaps. These last compounds may be suspended in water or oil-in-water emulsions in finely divided form or may be dissolved in other solvents and then incorporated in the water or oil emulsions and the like, provided that care is taken to employ a solvent whlchis non-injurious to the plant to which the spray is to be applied.

The relatively insoluble compounds will generally be found to fall within theclass represented by the formula RmPbXn, wherein both m and 1: represent the integer 2. The compounds falling within the formula RsPbX will generally be found to be the most effective and the most soluble and will generally be preferred.

In general, the compounds of our invention are old and well known chemical compounds and the methods oi making them are also well known and are described in the literature.

While we have disclosed specific embodiments of our invention. it will be readily apparent to those skilled in the art that many variations and modifications may be made therein and the proportions employed without departing trom the spirit of our invention. Accordingly, the scope of our invention is to be limited solely by the appended claims, construed as broadly, as is permissible in view ot the prior art.

We claim:

1. An insecticidal spray material comprising an aqueous liquid having incorporated therein a compound of the type:

RmPbXn wherein R represents an unsubstituted hydrocarbon radical, X represents an acid radical, 1n represents at least 2, n represents at least 1. and m plus 1: equals 4.

2. An insecticidal spray material comprising an. 10 aqueous liquid having incorporated therein a compound oi the type RsPbX wherein R represents an unsubstituted hydrocar- .bon radical and X represents an acid radical.

3. An insecticidal spray material comprising water having incorporated therein an amine soap and a compound of the type:

RmPbXn wherein R represents an unsubstituted hydrocarbon radical, X represents an acid radical, m represents at least 2, n represents at least 1, and m plus n equals 4. 4. An insecticidal spray material comprising an oil in water emulsion having incorporated therein a compound of the type:

RmPbXn wherein R represents an unsubstituted hydrocarbon radical, X represents an acid radical, m

represents at least 2, n represents at least 1, and

m plus 11 equals 4. 5. An insecticidal spray material comprising an 85 aqueous liquid having incorporated therein a compound of the type:

RmPbXn wherein R represents an unsubstituted hydrocarbon radical, X represents an oleic acid radical, m represents at least 2, n represents at least 1. and m plus :1 equals 4.

6. An insecticidal spray material comprising. an aqueous liquid having incorporated therein a compound of the type:

RaPbX wherein R represents an unsubstituted hydrocarbon radical and X represents an oleic acid radical.

7. The method of exterminating insects which comprises spraying the insects with an aqueous liquid having incorporated therein a compound of the type:

' RmPbXn wherein R represents an unsubstituted hydrocarbon radical, X represents an acid radical, m represents at least 2, n represents at least 1, and m plus n equals 4.

8. The method of exterminating insects which comprises spraying theinsects with an aqueous liquid having incorporated therein a compound of the type:

RaP'bX whereinR represents an unsubstituted hydrocar bon radical and X represents an acid radical.

WILLIAM s. CALCO'I'I. WENDELL H. 'rrsnam. mam L. mama. 

